Combatting pests with O-ethyl-S-n-propyl-O-(substituted phenyl)-phosphorothiolates

ABSTRACT

Combating insects, acarids and nematodes with O-ethyl-S-n-propyl-O-(substituted phenyl)-phosphorothiolates of the general formula ##STR1## wherein X is halogen, lower alkyl, nitro, cyano, lower alkylmercapto, lower alkylsulfinyl, lower alkoxycarbonyl or lower alkyl carbonyl, and 
     m is 1, 2 or 3.

This is a division of application Ser. No. 448,587, filed Mar. 6, 1974, now U.S. Pat. No. 3,954,919, issued May 4, 1976, which is a division of Ser. No. 208,902, filed Dec. 16, 1971, now U.S. Pat. No. 3,839,511, issued Oct. 1, 1974.

The present invention relates to and has for its objects the provision of particular new O-ethyl-S-n-propyl-O-(substituted phenyl)-phosphorothiolates, i.e. those wherein the phenyl group carries 1, 2 or 3 halogen, lower alkyl, nitro, cyano, lower alkylmercapto, lower alkylsulfinyl, lower alkoxycarbonyl or lower alkylcarbonyl groups, which possess insecticidal, acaricidal and nematocidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. insects, acarids, and nematodes, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known that O,S-dialkyl-O-phenylphosphorothiolates exhibit insecticidal activity. However, this activity is so low that they have not been used in spite of being less toxic to warm-blooded animals than the corresponding O,O-dialkyl-O-phenylphosphorothioates.

For example, O,O-dimethyl-O-4-nitrophenylphosphorothioate (Compound A; common name, methylparathion) of the following formula: ##STR2## has strong insecticidal activity and exhibits excellent effects, while the corresponding O,S-dimethyl-4-nitrophenyl phosphorothiolate (Compound B) of the formula: ##STR3## which has only one-third of the toxicity to warm-blooded animals has unfortunately only one-fiftieth of the insecticidal activity.

As methylparathion is very toxic to warm-blooded animals, much research has been conducted with a view to developing a novel effective insecticide with low toxicity to warm-blooded animals and has resulted in the provision of O,O-dimethyl-O-(3-methyl-4-nitrophenyl)phosphorothioate (Compound C; commercial name, Sumithion) and O,O-dimethyl-O-(3-methyl-4-methylthiophenyl)-phosphorothioate (Compound D; commercial name, Lebaycid).

These phosphorothioates have been widely used as insecticides, but difficulty has been found in controlling harmful insects which have acquired resistance to these insecticides. In such circumstances, there is a strong demand for a novel insecticide effective against resistant harmful insects.

The present invention provides compounds which have great insecticidal activity, only slight toxicity for warm-blooded animals and practically no phytotoxicity, so that they can be used for controlling a great variety of harmful insects, such as harmful sucking insects, biting insects, plant parasites, hygiene pest insects and stored-grain insects.

The present invention is based on the surprising discovery that those O-alkyl-S-alkyl-O-phenylphosphorothiolates in which the alkyl groups are different and in which the alkyl attached to the S atom is n-propyl and the O-alkyl is ethyl have excellent insecticidal activity, very much greater for example than if the two alkyls have the same number of carbon atoms or if the alkyl attached to the S atom is alkyl other than n-propyl.

The present invention accordingly provides particular O-ethyl-S-n-propyl-O-phenyl phosphorothiolates of the following general formula: ##STR4## wherein X is halogen, lower alkyl, nitro, cyano, lower alkylmercapto, lower alkylsulfinyl, lower alkoxycarbonyl or lower alkyl carbonyl, and

m is 1, 2 or 3.

The invention also provides a process for the production of a compound according to the invention in which

(a) a thiol phosphoric acid diester halide of the general formula: ##STR5## is reacted with a phenol of the general formula: ##STR6##

(b) a compound of the general formula: ##STR7## is reacted with an oxidizing agent, or

(c) a salt of a thiophosphoric acid of the general formula: ##STR8## is reacted with a halide of the formula:

    Hal-C.sub.3 H.sub.7 -n                                     (V)

in which formulae

Hal is halogen,

M¹ is hydrogen or a metal or ammonium,

M² is metal or ammonium,

R is lower alkyl, and

X and m have the meanings stated

with respect to formula (I).

Process variant (a) is illustrated by the following formula scheme: ##STR9##

Examples of X are lower alkyl groups such as methyl, ethyl, n-(or iso-) propyl, n-(or iso-, sec.- or tert.-) butyl; halogen atoms such as fluorine, chlorine, bromine or iodine; nitro, cyano, lower alkylmercapto or lower alkylsulfinyl groups; lower alkoxycarbonyl or lower alkylcarbonyl groups.

Hal is preferably chlorine. M¹ may be ammonium, hydrogen, sodium, potassium or lithium.

Examples of the compounds of formula (III) include:

2-(or 3- or 4-)chloro (or bromo)phenol,

2,4-(or 2,5- or 2,6-)dichlorophenol,

2,4-dibromophenol,

2,4,5-(or 2,4,6-)trichlorophenol,

2,5-dichloro-4-bromophenol,

2-(or 3- or 4-)methylphenol,

4-ethylphenol,

2-iso-propylphenol,

4-tert.-butylphenol,

2-sec.-butylphenol,

2,4-(or 3,4- or 3,5-)dimethylphenol,

2-iso-propyl-5-methylphenol,

2-chloro-4-(or 5- or 6-)methylphenol,

4-chloro-2-(or 3-)methylphenol,

2-chloro-4-tert.-butylphenol,

4-chloro-3,5-dimethylphenol,

2,4-dichloro-6-methylphenol,

2-(or 3- or 4-)nitrophenol,

2-(or 3-)chloro-4-nitrophenol,

3-methyl-4-nitrophenol,

3-nitro-4-(or 6-)methylphenol,

2-nitro-4-chlorophenol,

2-nitro-4-methylphenol,

2,6-dichloro-4-nitrophenol,

3-nitro-4-chlorophenol,

2-(or 4-)cyanophenol,

2-chloro-4-cyanophenol,

2-cyano-4-chlorophenol,

2-cyano-4,6-dichlorophenol,

2-(or 4-)ethoxycarbonylphenol,

2-chloro-4-ethoxycarbonylphenol,

2,6-dichloro-4-ethoxycarbonylphenol,

2-methoxycarbonylphenol,

2-ethoxycarbonyl-4-chlorophenol,

2-ethoxycarbonyl-4,6-dichlorophenol,

2-(or 4-)methylcarbonylphenol,

2,6-dichloro-4-methylcarbonylphenol,

2-chloro-4-methylmercaptophenol,

4-methylmercaptophenol,

4-ethylmercaptophenol,

2-methyl-4-methylmercaptophenol,

3-methyl-4-methylmercaptophenol,

3,5-dimethyl-4-methylmercaptophenol,

4-methylsulfinylphenol,

2-methyl-4-methylsulfinylphenol,

3,5-dimethyl-4-methylsulfinylphenol.

Sodium or potassium salts of the corresponding phenols may be used.

In the production of the compounds of this invention according to the above method, the reaction is preferably conducted in a solvent or diluent. For this purpose any inert solvent or diluent may be used.

As the solvent or diluent there may be cited water; aliphatic, alicyclic and aromatic hydrocarbons which may be chlorinated such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, mono-, di-, and tri-chloroethylenes, and chlorobenzene; ethers such as diethyl ether, methyl ethyl ether, di-iso-propyl ether, dibutyl ether, ethylene oxide, dioxane and tetrahydrofurane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; nitriles such as acetonitrile propionitrile and acrylonitrile; alcohols such as methanol, ethanol, isopropanol, butanol and ethylene glycol; esters such as ethyl acetate and amyl acetate; amides such as dimethyl formamide and dimethyl acetamide; and sulfoxides and sulfones such as dimethyl sulfoxide and sulfolane.

This process variant may be carried out in the presence of an acid binder according to need. As the acid binder there may be cited hydroxides, carbonates, bicarbonates and alcoholates of alkali metals and tertiary amines such as triethylamine, diethylaniline and pyridine.

In this process variant, the reaction may be effected at temperatures over a broad range, but generally the reaction is carried out at temperatures ranging from about -20° C. to the boiling point of the reaction mixture, preferred temperatures being in the range from about 10° to 100° C.

Process variant (c) is illustrated by the following formula scheme: ##STR10##

Examples of the salts of O-ethyl-O-substituted phenyl thiophosphoric acid of the formula (IV) used as starting material include:

O-ethyl-O-[2- (or 3- or 4-)chlorophenyl]-,

O-ethyl-O-[2- (or 4-)bromophenyl]-,

O-ethyl-O-[2- (or 3- or 4-)methylphenyl]-,

O-ethyl-O-(4-ethylphenyl)-,

O-ethyl-O-(2-iso-propylphenyl)-,

O-ethyl-O-(4-tert.-butylphenyl)-,

O-ethyl-O-(2-sec.-butylphenyl)-,

O-ethyl-O-(4-methylmercaptophenyl)-,

O-ethyl-O-(4-ethylmercaptophenyl)-,

O-ethyl-O-(4-methylsulfinylphenyl)-,

O-ethyl-O-[2-(3- or 4-)nitrophenyl]-,

O-ethyl-O-[2-(2-(or 4-)cyanophenyl]-,

O-ethyl-O-(2-methoxycarbonylphenyl)-,

O-ethyl-O-[2-(or 4-)methylcarbonylphenyl]-,

O-ethyl-O-[2-(or 4-)ethoxycarbonylphenyl]-,

O-ethyl-O-[2,4-(or 2,5- or 2,6-)dichlorophenyl]-,

O-ethyl-O-(2,4-dibromophenyl)-,

O-ethyl-O-[2,4-(3,4- or 3,5-)dimethylphenyl]-,

O-ethyl-O-(2-iso-propyl-5-methylphenyl)-,

O-ethyl-O-(2-chloro-4-methylphenyl)-,

O-ethyl-O-(2-chloro-6-methylphenyl)-,

O-ethyl-O-(2-chloro-5-methylphenyl)-,

O-ethyl-O-(2-methyl-4-chlorophenyl)-,

O-ethyl-O-(3-methyl-4-chlorophenyl)-,

O-ethyl-O-(2-chloro-4-tert.-butylphenyl)-,

O-ethyl-O-(3-methyl-4-methylmercaptophenyl)-,

O-ethyl-O-(2-chloro-4-nitrophenyl)-,

O-ethyl-O-(3-chloro-4-nitrophenyl)-,

O-ethyl-O-(3-methyl-4-nitrophenyl)-,

O-ethyl-O-(3-nitro-4-methylphenyl)-,

O-ethyl-O-(2-methyl-5-nitrophenyl)-,

O-ethyl-O-(2-nitro-4-chlorophenyl)-,

O-ethyl-O-(2-nitro-4-methylphenyl)-,

O-ethyl-O-(3-nitro-4-chlorophenyl)-,

O-ethyl-O-(2-chloro-4-cyanophenyl)-,

O-ethyl-O-(2-cyano-4-chlorophenyl)-,

O-ethyl-O-(2-chloro-4-ethoxycarbonylphenyl)-,

O-ethyl-O-(2-ethoxycarbonyl-4-chlorophenyl)-,

O-ethyl-O-(2,6-dichloro-4-methylcarbonylphenyl)-,

O-ethyl-O-(2-chloro-4-methylmercaptophenyl)-,

O-ethyl-O-(2-methyl-4-methylmercaptophenyl)-,

O-ethyl-O-(2-methyl-4-methylsulfinylphenyl)-,

O-ethyl-O-(2,4,5-trichlorophenyl)-,

O-ethyl-O-(2,5-dichloro-4-bromophenyl)-,

O-ethyl-O-(2,4,6-trichlorophenyl)-,

O-ethyl-O-(3,5-dimethyl-4-chlorophenyl)-,

O-ethyl-O-(2,4-dichloro-6-methylphenyl)-,

O-ethyl-O-(2,6-dichloro-4-nitrophenyl)-,

O-ethyl-O-(2-cyano-4,6-dichlorophenyl)-,

O-ethyl-O-(2,6-dichloro-4-ethoxycarbonylphenyl)-,

O-ethyl-O-(2-ethoxycarbonyl-4,6-dichlorophenyl)-,

O-ethyl-O-(3,5-dimethyl-4-methylmercaptophenyl)-, or

O-ethyl-O-(3,5-dimethyl-4-methylsulfinylphenyl)-

thiophosphoric acid potassium salt and the corresponding sodium and ammonium salts.

Examples of the n-propylhalide of the formula (V) used as starting material include n-propylbromide and the corresponding chlorides.

This process variant may be carried out in the same manner as process variant (a), and the compound of the present invention can be obtained with high purity and in high yield.

As mentioned above, the compounds of the present invention can be used for controlling harmful insects of a broad range such as those belonging to

    ______________________________________                                         Coleoptera                                                                     such as Rice weevil     Sitophilus oryzae                                              Rust-red beetle Tribolium castaneum                                            28-spotted lady beetle                                                                         Epilachana vigintiocto-                                                        punctata                                                       Barley wireworm Agriotes fuscicollis                                           Soy bean beetle Anomala rufocuprea                                     Lepidoptera                                                                    such as Gypsy moth      Lymantria dispar                                               Tent caterpillar                                                                               Malacosoma neustria                                                            testacea                                                       Common cabbageworm                                                                             Pieris rapae crucivo ra                                        Tobacco cutworm Prodenia litura                                                Rice-stem borer Chilo suppressalis                                             Smaller tea tortrix                                                                            Adoxophyes orana                                               Almond moth     Ephestia cautella                                      Hemiptera                                                                      such as Green rice leafhopper                                                                          Nephotettix cincticeps                                         Brown planthopper                                                                              Nilaparvata lugens                                             Comstock mealybug                                                                              Pseudococcus comstocki                                         Arrowhead scale Unaspis yanonensis                                             Green peach aphid                                                                              Myzus persicae                                                 Apple aphid     Aphis pomi                                                     Cabbage aphid   Brevicoryne brassicae                                  Orthoptera                                                                     such as German cockroach                                                                               Blatella germanica                                             American cockroach                                                                             Periplaneta americana                                          African mole cricket                                                                           Gryllotalpa africana                                   Isoptera                                                                       such as Japanese termite                                                                               Leucotermes speratus                                   Diptera                                                                        such as House fly       Musca domestica vicina                                         Yellow fever mosquito                                                                          Aedes aegypti                                                  Seed-corn maggot                                                                               Hylemya platura                                                Common mosquito Culex pipiens                                                  Malaria mosquito                                                                               Anopheles simensis                                             Japanese encephalistis                                                                         Culex tritaeniorhynchus                                Acarina                                                                        such as Carmine mite    Tetranychus telarius                                           Citrus red mite Panonychus citri                                               Japanese citrus red mite                                                                       Aculus pelekassi                                       Nematode                                                                       such as Southern root-knot                                                                             Meloidogyne incognita                                          nematode                                                                       Rice white-tip nematode                                                                        Aphelenchoides besseyi                                         Soy bean cyst nematode                                                                         Heterodera glycines                                    ______________________________________                                    

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbon (e.g. benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), cycloalkanes (e.g. cyclohexane, etc.), paraffins (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other insecticides, acaricides, and nematocides, or rodenticides, fungicides, bactericides, herbicides, fertilizers, growth-regulating agents, antibiotics, antiviral agents, or attractants, e.g. organic phosphorous acid esters, carbamates, dithio- or (thiol) carbamates, chlorinated compounds, dinitro compounds, organic sulfur or metal compounds, substituted diphenyl ethers, anilides, urea, triazines, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1-95% by weight, and preferably 0.5-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-20%, preferably 0.005-10%, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001-95%, and preferably 0.005-95%, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 15 to 1000 g/hectare, preferably 40 to 600 g/hectare, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight of the active compound or even the 100% active substance alone, e.g. about 20-100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects, acarids, fungi, bacteria and yeasts, and more particularly methods of combating at least one of insects and acarids, which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, (c) such nematodes and (d) the corresponding habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. an insecticidally, acaricidally or nematocidally effective amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above.

The formulations and ready-to-use preparations may be applied in the usual manner, for instance by spraying (such as liquid spraying), misting, atomizing, dusting, scattering, watering, pouring, fumigating, soil application (such as mixing, sprinkling, vaporizing, irrigating), by surface application (such as painting, banding, dressing), by dipping or in the form of baits.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The invention is illustrated by the following Examples, comprising preparative Examples 1 to 6, formulation Examples 7 to 12 and test Examples 13 to 19. In the formulation and test Examples, individual compounds according to the invention are identified by numbers corresponding to those in Table 1 following Example 6.

EXAMPLE 1 Synthesis of S-n-propyl-O-ethylchloride phosphorothiolate ##STR11##

19.3 of S-n-propyldichloride phosphorothiolate were dissolved in 100 ml of benzene, into which a mixture consisting of 4.6 g of ethanol, 10.1 g of triethylamine and 20 ml of benzene was dropped while stirring at a temperature no higher than 0° C. Upon completion of the addition, the reaction mixture was stirred at room temperature for 2 hours to complete the reaction. Then the reaction mixture was separated by filtration and the filtrate was concentrated by distillation. The residue thus obtained was distilled under reduced pressure, whereby 15 g of S-n-propyl-O-ethylchloride phosphorothiolate was obtained. Boiling point: 70°-74° C./0.4 mm Hg. Refractive index n_(D) ²⁰ = 1.4901. ##STR12##

15 g of 4-tert.-butyl phenol were dissolved in 150 ml of benzene, to which 10.1 g of triethylamine were added. 20.3 g of S-n-propyl-O-ethylchloride phosphorothiolate were added dropwise into the mixture while stirring at a temperature no higher than 10° C. Upon completion of the addition, the mixture was stirred for a while at room temperature and was then heated at 65° C. for 3 hours with stirring. Upon completion of the reaction, the mixture was washed with water, 1% hydrochloric acid, 1% sodium carbonate and water in the order mentioned and dried over anhydrous sodium sulfate. After removal of benzene by distillation, the residue was distilled under reduced pressure, whereby O-ethyl-O-(4-tert.-butylphenyl)-S-n-propyl phosphorothiolate was obtained in an amount of 25 g. Boiling point: 155°-156° C./0.07 mm Hg.

Refractive index n_(D) ²⁰ = 1.5111.

EXAMPLE 2 ##STR13##

13.9 g of 4-nitrophenol were dissolved in 150 ml of benzene, to which 10.1 g of triethylamine were added. 20.3 g of S-n-propyl O-ethylchloride phosphorothiolate were dropped into the mixture while stirring at a temperature no higher than 10° C. Upon completion of the addition, the mixture was stirred for a while at room temperature and was then heated at 65° C. for 3 hours with stirring. Upon completion of the reaction, the mixture was washed with water, 1% hydrochloric acid, 1% sodium carbonate and water in the order mentioned and dried over anhydrous sodium sulfate. After removal of benzene by distillation, the residue was distilled under reduced pressure, whereby O-ethyl-O-(4-nitrophenyl)-S-n-propyl phosphorothiolate was obtained in an amount of 24 g. Boiling point: 159°-161° C./0.025 mm Hg.

Refractive index n_(D) ²⁰ = 1.5424.

EXAMPLE 3 Synthesis of the potassium salt of O-ethyl-O-(4-methylthiophenyl)thiophosphoric acid ##STR14##

41 g of potassium hydroxide were dissolved in 200 ml of water, to which 250 ml of dioxane were added. While stirring vigorously, 102 g of O-ethyl-O-(4-methylthiophenyl)thionophosphoryl chloride were dropped in at 30°-40° C. Upon completion of the adding, the mixture was further stirred continuously for 1 hour at 60° C. to complete the reaction.

The dioxane and water were distilled off under reduced pressure and the residue was dissolved in water again. Benzene was then added to the solution. The mixture was shaken. The aqueous part was concentrated under reduced pressure and the residue was dissolved in acetone and the inorganic salt was separated by filtration. After the acetone had been distilled off, toluene was added to the residue and the precipitate formed was separated by filtration, whereby 85 g of crude potassium O-ethyl-O-(4-methylthiophenyl)-S-n-propyl phosphorothiolate were obtained.

EXAMPLE 3 ##STR15##

30.2 g of the potassium salt of O-ethyl-O-(4-methylthiophenyl) thiophosphoric acid were dissolved in 80 ml of alcohol, to which 13 g of n-propylbromide were added. The mixture was stirred for 4 hours at 60° C. and the inorganic salt formed was separated by filtration. After the alcohol had been distilled off the residue was dissolved in benzene and washed with water, 1% sodium carbonate and water in the order mentioned. After drying with Na₂ SO₄, the benzene was distilled off and the residue was distilled under reduced pressure, whereby 25 g of O-ethyl-O-(4-methylthiophenyl)-S-n-propyl phosphorothiolate were obtained.

Boiling point: 145°-152° C./0.05 mm Hg. Refractive index n_(D) ²⁰ = 1.5515.

EXAMPLE 4 Synthesis of potassium O-ethyl-O-(2,4-dichlorophenyl)-thiophosphate ##STR16##

34 g of potassium hydroxide were dissolved in 200 ml of water, to which 200 ml of dioxane were added. While the mixture was being vigorously stirred, 92 g of O-ethyl-O-(2,4-dichlorophenyl)thiophosphoryl chloride were dropped in at 30°-40° C. Upon completion of the addition, the temperature was gradually raised and the mixture was further stirred continuously for 1 hour at 60°-70° C. to complete the reaction.

The dioxane and water were distilled off under reduced pressure and the residue was dissolved in acetone and the inorganic salt was separated by filtration. After distilling acetone off, toluene and n-hexane were added to the residue and the precipitate formed was separated by filtration, whereby 75 g of crude potassium O-ethyl-O-(2,4-dichlorophenyl) thiophosphate were obtained. ##STR17##

32.5 g of potassium salt of O-ethyl-O-(2,4-dichlorophenyl) thiophosphoric acid were dissolved in 70 ml of alcohol, to which 13 g of n-propyl bromide were added. The mixture was stirred for 3 hours at 70° C. and the inorganic salt formed was separated by filtration. After the alcohol had been distilled off, the residue was dissolved in benzene and washed with water and 1% sodium carbonate. After drying with Na₂ SO₄, the benzene was distilled off and the residue was distilled under reduced pressure whereby 27 g of O-ethyl-O-(2,4-dichlorophenyl)-S-n-propyl phosphorothiolate were obtained.

Boiling point: 155°-165° C./0.25 mm Hg. Refractive index n_(D) ²⁰ = 1.5362.

EXAMPLE 5 ##STR18##

15.3 g of O-ethyl-O-(4-methylthiophenyl)-S-n-propyl-phosphorothiolate, produced in Example 3 (b), were dissolved in 60 ml of glacial acetic acid. 6 g of 30% hydrogen peroxide solution were added dropwise while the reaction temperature was maintained at 20°-30° C. with external cooling. After the completion of the addition, the reaction mixture was stirred for 1 hour and then heated at 40° C. for 30 minutes to complete the reaction. The reaction mixture was diluted with water and benzene and then it was shaken. The benzene layer was washed sequentially with water, 1% sodium carbonate solution and water, and then dried over anhydrous sodium sulfate. After the benzene had been distilled off, 14 g of light yellowish oily O-ethyl-O-(4-methylsulfinylphenyl)-S-n-propyl-phosphorothiolate, n_(D) ²⁰ = 1.5496, were obtained.

EXAMPLE 6

The following Table 1 contains a list of compounds according to the invention. These compounds can be prepared by methods analogous to those described in Example 1-5.

                  Table 1                                                          ______________________________________                                          ##STR19##                                                                     ______________________________________                                         Com-                                                                           pound X.sub.m    Physical Properties                                           ______________________________________                                         1     2-Cl       b.p. 132 - 143° C./0.2mmHg                                                                n.sub.D.sup.20 1.5276                       2     3-Cl       b.p. 130 - 136° C./0.1mmHg                                                                n.sub.D.sup.20 1.5243                       3     4-Cl                         n.sub.D.sup.20 1.5262                       4     2-Br       b.p. 140 - 147° C./0.1mmHg                                                                n.sub.D.sup.20 1.5467                       5     4-Br       b.p. 136 - 140° C./0.15mmHg                                                               n.sub.D.sup.20 1.5503                       6     2-CH.sub.3 b.p. 116 - 119° C./0.08mmHg                                                               n.sub.D.sup.20 1.5192                       7     3-CH.sub.3 b.p. 132 - 139° C./0.08mmHg                                                               n.sub.D.sup.20 1.5209                       8     4-CH.sub.3 b.p. 125 - 133° C./0.1mmHg                                                                n.sub.D.sup.20 1.5191                       9     4-C.sub.2 H.sub.5                                                                         b.p. 133 - 137° C./0.1mmHg                                                                n.sub.D.sup.20 1.5183                       10    2-iso-C.sub.3 H.sub.7                                                                     b.p. 119 - 121°C./0.08mmHg                                                                n.sub.D.sup.20 1.5120                       11    4-tert-C.sub.4 H.sub.9                                                                    b.p. 155 - 156° C./0.07mmHg                                                               n.sub.D.sup.20 1.5111                       12    2-sec-C.sub.4 H.sub.9                                                                     b.p. 145 - 149° C./0.1mmHg                                                                n.sub.D.sup.20 1.5103                       13    4-CH.sub.3 S                                                                              b.p. 145 - 152° C./0.05mmHg                                                               n.sub.D.sup.20 1.5515                       14    4-C.sub.2 H.sub.5 S                                                                       b.p. 148 - 153° C./0.1mmHg                                                                n.sub.D.sup.20 1.5483                       15                                                                                   n.sub.D.sup.20 1.5496                                                    16    4-NO.sub.2 b.p. 159 - 161° C./0.25mmHg                                                               n.sub.D.sup.20 1.5424                       17    3-NO.sub.2 b.p. 153 - 158° C./0.2mmHg                                                                n.sub.D.sup.20 1.5421                       18    2-NO.sub.2 b.p. 151 - 155° C./0.9mmHg                                                                n.sub.D.sup.20 1.5351                       19    4-CN       b.p. 145 - 149° C./0.15mmHg                                                               n.sub.D.sup.20 1.5293                       20    2-CN       b.p. 143 - 147° C./0.15mmHg                                                               n.sub.D.sup.20 1.5290                       21                                                                                   b.p. 160 - 162° C./0.25mmHg                                                        n.sub.D.sup.20 1.5152                                         22                                                                                   b.p. 153 - 156° C./0.25mmHg                                                        n.sub.D.sup.20 1.5193                                         23                                                                                   b.p. 156 - 159° C./0.2mmHg                                                         n.sub.D.sup.20 1.5137                                         24                                                                                   b.p. 166 - 169° C./0.15mmHg                                                        n.sub.D.sup.20 1.5365                                         25                                                                                   b.p. 155 - 157° C./0.1mmHg                                                         n.sub.D.sup.20 1.5388                                         26    2,4-Cl.sub.2                                                                              b.p. 155 - 165° C./0.25mmHg                                                               n.sub.D.sup.20 1.5362                       27    2,5-Cl.sub.2                                                                              b.p. 141 - 146° C./0.1mmHg                                                                n.sub.D.sup.20 1.5419                       28    2,6-Cl.sub.2                                                                              b.p. 141 - 145° C./0.15mmHg                                                               n.sub.D.sup.20 1.5477                       29    2,4-Br.sub.2                                                                              b.p. 154 - 159° C./0.06mmHg                                                               n.sub.D.sup.20 1.5688                       30    2,4-(CH.sub.3).sub.2                                                                      b.p. 128 - 131° C./0.1mmHg                                                                n.sub.D.sup.20 1.5160                       31    3,4-(CH.sub.3).sub.2                                                                      b.p. 130 - 132° C./0.08mmHg                                                               n.sub.D.sup.20 1.5270                       32    3,5-(CH.sub.3).sub.2                                                                      b.p. 121 - 123° C./0.05mmHg                                                               n.sub.D.sup.20 1.5178                       33    2-iso-C.sub.3 H.sub.7,                                                                    b.p. 125 - 128° C./0.07mmHg                                                               n.sub.D.sup.20 1.5103                             5-CH.sub.3                                                               34    2-Cl, 4-CH.sub.3                                                                          b.p. 144 -  151° C./0.1mmHg                                                               n.sub.D.sup.20 1.5291                       35    2-Cl, 6-CH.sub.3                                                                          b.p. 133 - 140° C./0.15mmHg                                                               n.sub.D.sup.20 1.5302                       36    2-Cl, 5-CH.sub.3                                                                          b.p. 130 - 134° C./0.15mmHg                                                               n.sub.D.sup.20 1.5312                       37    4-Cl, 2-CH.sub.3                                                                          b.p. 132 - 136° C./0.1mmHg                                                                n.sub.D.sup.20 1.5328                       38    4-Cl, 3-CH.sub.3                                                                          b.p. 145 - 151° C./0.2mmHg                                                                n.sub.D.sup.20 1.5281                       39    2-Cl,      b.p. 144 - 146° C./0.1mmHg                                                                n.sub.D.sup.20 1.5230                             4-tert-C.sub.4 H.sub.9                                                   40    3-CH.sub.3,                                                                               b.p. 158 - 160° C./0.1mmHg                                                                n.sub.D.sup.20 1.5609                             4-CH.sub.3 S                                                             41    2-Cl, 4-NO.sub.2                                                                          b.p. 160 - 162° C./0.1mmHg                                                                n.sub.D.sup.20 1.5455                       42    3-Cl, 4-NO.sub.2                                                                          b.p. 170 - 175° C./0.25mmHg                                                               n.sub.D.sup.20 1.5450                       43    3-CH.sub.3, 4-NO.sub.2                                                                    b.p. 164 - 168° C./0.07mmHg                                                               n.sub.D.sup.20 1.5400                       44    3-NO.sub.2, 4-CH.sub.3                                                                    b.p. 147 - 152° C./0.1mmHg                                                                n.sub.D.sup.20 1.5308                       45    2-CH.sub.3, 5-NO.sub.2                                                                    b.p. 160 - 164° C./0.06mmHg                                                               n.sub.D.sup.20 1.5373                       46    2-NO.sub.2, 4-Cl                                                                          b.p. 155 - 157° C./0.08mmHg                                                               n.sub.D.sup.20 1.5479                       47    2-NO.sub.2, 4-CH.sub.3                                                                    b.p. 156 - 157° C./0.15mmHg                                                               n.sub.D.sup.20 1.5318                       48    3-NO.sub.2, 4-Cl                                                                          b.p. 160 - 164° C./0.1mmHg                                                                n.sub.D.sup.20 1.5471                       49    2-Cl, 4-CN b.p. 157 - 161° C./0.1mmHg                                                                n.sub.D.sup.20 1.5544                       50    2-Cn, 4-Cl b.p. 145 - 147° C./0.06mmHg                                                               n.sub.D.sup.20 1.5460                       51                                                                                   b.p. 160 - 164° C./0.2mmHg                                                         n.sub.D.sup.20 1.5289                                         52                                                                                   b.p. 160 - 164° C./0.15mmHg                                                        n.sub.D.sup.20 1.5216                                         53                                                                                   b.p. 173 - 176° C./0.15mmHg                                                        n.sub.D.sup.20 1.5462                                         54    2-CH.sub.3,                                                                               b.p. 156 - 160° C./0.05mmHg                                                               n.sub.D.sup.20 1.5509                             4-CH.sub.3 S                                                             55                                                                                   n.sub.D.sup.20 1.5489                                                    56    2,4,5-Cl.sub. 3                                                                           b.p. 142 - 148° C./0.15mmHg                                                               n.sub.D.sup.20 1.5480                       57    2,5-Cl.sub.2, 4-Br                                                                        b.p. 161 - 165° C./0.15mmHg                                                               n.sub.D.sup.20 1,5674                       58    2,4,6-Cl.sub.3                                                                            b.p. 143 - 145° C./0.08mmHg                                                               n.sub.D.sup.20 1.5496                       59    3,5-(CH.sub.3).sub.2,                                                                     b.p. 144 - 148° C./0.1mmHg                                                                n.sub.D.sup.20 1.5690                             4-Cl                                                                     60    2,4-Cl.sub.2, 6-CH.sub.3                                                                  b.p. 138 - 140° C./0.1mmHg                                                                n.sub.D.sup.20 1.5408                       61    2,6-Cl.sub.2,                                                                             b.p. 181 - 185° C./0.12mmHg                                                               n.sub.D.sup.20 1.5660                             4-NO.sub.2                                                               62    2-Cn, 4,6-Cl.sub.2                                                                        b.p. 172 - 175° C./0.15mmHg                                                               n.sub.D.sup.20 1.5569                       63                                                                                   b.p. 176 - 180° C./0.1mmHg                                                         n.sub.D.sup.20 1.5347                                         64                                                                                   b.p. 169 - 171° C./0.15mmHg                                                        n.sub.D.sup.20 1.5341                                         65    4-CH.sub.3 S-,                                                                            b.p. 148 - 150° C./0.05mmHg                                                               n.sub.D.sup.20 1.5470                             3,5-(CH.sub.3).sub.2                                                     66                                                                                   n.sub.D.sup.20 1.5524                                                    67    2-Cl, 4-CH.sub.3 S                                                                        b.p. 153 - 158° C./0.1mmHg                                                                n.sub.D.sup.20 1.5650                       ______________________________________                                    

EXAMPLE 7

Wettable powder:

15 parts by weight of compound No. 26, 80 parts by weight of a mixture of diatomaceous earth and clay (1:5) and 5 parts by weight of the emulsifier "Runnox" (polyoxyethylene alkylaryl ether) are mixed and crushed to give a wettable powder. This formulation may be diluted with water to a concentration of 0.05% and may be applied by spraying on insects and/or their habitat.

EXAMPLE 8

Emulsifiable concentrate:

30 parts by weight of compound No. 13, 30 parts by weight of xylene, 30 parts by weight of "Kawakasol" (aliphatic hydrocarbons with a high boiling point) and 10 parts by weight of the emulsifier "Sorpol" (polyoxyethylene alkylaryl ether) are mixed and stirred to give an emulsifiable concentrate. This formulation may be diluted with water to a concentration of 0.05% and may be applied by spraying on insects and/or their habitat.

EXAMPLE 9

Dust:

2 parts by weight of compound No. 21 and 98 parts by weight of a mixture of talc and clay (1:3) are mixed and crushed to give a dust. This formulation may be applied by dusting on insects and/or their habitat.

EXAMPLE 10

Dust:

1.5 parts by weight of compound No. 5, 2 parts by weight of isopropyl hydrogen phosphate (PAP) and 96.5 parts by weight of a mixture of talc and clay (1:3) are mixed and crushed to give a dust. This formulation may be applied by dusting on insects and/or their habitat.

EXAMPLE 11

Granule:

10 parts by weight of compound No. 16, 10 parts by weight of bentonite, 78 parts by weight of a mixture of talc and clay (1:3) and 2 parts by weight of lignin sulphite are mixed. To this mixture 25 parts by weight of water are added and then the mixture is kneaded. It is cut into granules of about 20 to 40 mesh by means of a granulating machine. The granules are then dried at a temperature of 40° to 50° C. to give a granular formulation. This formulation may be applied by scattering on insects and/or their habitat.

EXAMPLE 12

Oil:

0.5 part by weight of compound No. 40, 20 parts by weight of Versicoal AR-50 (aromatic hydrocarbons with a high boiling point) and 79.5 parts by weight of Deobase (deodorized kerosene) are mixed and stirred to give an oily formulation. This formulation may be applied by spraying on insects and/or their habitat.

EXAMPLE 13

Tobacco cutworm or cotton leaf worm (Prodenia litura) larvae test

Solvent: 3 parts by weight of dimethyl formamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of the active compound, 1 part by weight of the active compound was thoroughly mixed with the stated amount of solvent and the emulsifier. The emulsifiable concentrate obtained was then diluted with water to the prescribed concentration.

Testing method:

Sweet potato leaves were dipped in the preparation of the active compound diluted to the prescribed concentration and were dried and put in a Petri dish of 9 cm diameter. 10 tobacco cutworm larvae were then placed in the dish. The dish was kept in a constant temperature chamber at 28° C. After 24 hours, the number of dead insects was counted and the killing ratio was calculated. The results are shown in Table 2.

                  Table 2                                                          ______________________________________                                         Test results against Prodenia litura larvae                                    ______________________________________                                                    Killing Ratio (%)                                                   Compound   Active Ingredient Concentration                                     No.        1000ppm    300ppm     100ppm                                        ______________________________________                                          1         100        100        100                                            2         100        100         80                                            3         100        100        100                                            4         100        100         90                                            5         100        100        100                                            6         100        100        100                                            7         100        100         60                                            8         100         90        --                                             9         100        100        --                                            10         100        100         60                                           11         100        100         50                                           12         100        100        --                                            13         100        100        100                                           14         100        100        100                                           15         100        100        100                                           16         100        100        100                                           17         100        100        100                                           18         100        100        --                                            19         100        100        100                                           20         100        100        --                                            21         100        100         90                                           22         100        100        100                                           23         100        100         90                                           24         100        100        --                                            25         100        100         60                                           26         100        100        100                                           27         100        100        100                                           28         100        100        100                                           29         100        100         80                                           30         100        100         90                                           31         100         90        --                                            32         100        100        100                                           33         100        100        100                                           34         100        100        100                                           35         100        100         80                                           36         100        100         80                                           37         100        100        100                                           38         100        100        100                                           39         100        100        100                                           40         100        100        100                                           41         100         80         50                                           42         100        100         90                                           43         100        100         90                                           44         100         90        --                                            45         100        100         60                                           46         100        100        --                                            47         100        100         80                                           48         100        100         60                                           49         100        100        100                                           50         100        100        100                                           51         100        100         60                                           52         100        100         90                                           53         100        100         80                                           54         100        100        --                                            55         100        100        --                                            56         100        100        100                                           57         100        100        100                                           58         100        100        100                                           59         100        100         80                                           60         100        100        100                                           61         100        100         80                                           62         100        100         80                                           63         100        100         50                                           64         100         90        --                                            65         100        100        --                                            66         100        100        --                                            67         100        100         90                                           ______________________________________                                         DEP*                                                                           (commercially                                                                  available                                                                      comparison)                                                                               100         25        0                                             MPP**                                                                          (commercially                                                                  available                                                                      comparison)                                                                                30         0         0                                             Untreated control      0                                                       ______________________________________                                           *DEP: O,O-dimethyl-1-hydroxy-2,2,2-trichloroethyl-phosphonate                 **MPP: O,O-dimethyl-O-[(4-methylmercapto-3-methyl)phenyl] phosphorothioat                                                                               

EXAMPLE 14

Fall webworm (Hyphantria cunea) larvae test

Testing method:

Mulberry leaves were dipped in the preparation of the active compound diluted to the prescribed concentration prepared in the same manner as in Example 13, and after drying in air, were placed in a Petri dish of 9 cm diameter. 10 fall webworms were then placed in the dish and the dish was kept in a constant temperature chamber at 25° C. After 24 hours, the number of dead insects was counted and the killing ratio was calculated. The results are shown in Table 3.

                  Table 3                                                          ______________________________________                                         Test results against Hyphantria cunea larvae                                   ______________________________________                                                    Killing Ratio (%)                                                   Compound   Active ingredient concentration                                     No.        1000ppm    300ppm     100ppm                                        ______________________________________                                          1         100        100        100                                            3         100        100        100                                            5         100         80         60                                           10         100         90        --                                            11         100        100         80                                           13         100        100         90                                           16         100        100         90                                           17         100        100        --                                            18         100         64         60                                           19         100         90         40                                           20         100        100         90                                           21         100         90         50                                           23         100        100         60                                           24         100        100         60                                           26         100        100        100                                           27         100        100         60                                           28         100         80         50                                           30         100        100        --                                            32         100        100        100                                           36         100        100        --                                            37         100        100         90                                           38         100        100         80                                           39         100        100         90                                           40         100        100        100                                           44         100         70         60                                           47         100        100        --                                            54         100        100        100                                           55         100        100        100                                           56         100        100         70                                           58         100        100        --                                            60         100        100         80                                           65         100        100        100                                           66         100        100        100                                           67         100         90         80                                           ______________________________________                                         MPP                                                                            (commercially                                                                  available                                                                      comparison)                                                                                90         0          0                                            Untreated control      0                                                       ______________________________________                                    

EXAMPLE 15

Rice stem borer (Chilo suppressalis) larvae test

Testing method:

Egg masses of the rice stem borer were attached to rice, at the tillering stage, planted in a pot of 12 cm diameter, and on the 7th day from the hatching, 40 ml of the preparation of the active compound diluted to the prescribed concentration (prepared in the same manner as in Example 13) were sprayed on to the rice. The rice was kept in a greenhouse. Three days later, the treated stem was examined by breaking it and the killing ratio was calculated from the surviving borers and killed borers. The results are shown in Table 4.

                  Table 4                                                          ______________________________________                                         Test results against Chilo suppressalis larvae                                 ______________________________________                                               Killing ratio (%)      Killing Ratio (%)                                 Com-  Active Ingredient                                                                             Com-    Active Ingredient                                 pound Concentration  pound   Concentration                                     No.   250ppm         No.     250ppm                                            ______________________________________                                          1    100            41      100                                                3    100            44      100                                                5    100            47      100                                                6    100            50      100                                               11    87.7           51      100                                               13    100            52      100                                               15    100            53      100                                               16    98.6           54      100                                               18    100            55      100                                               19    100            56      100                                               20    100            58      94.7                                              21    100            60      100                                               23    95.5           65      100                                               24    100            66      100                                               26    100                                                                      27    100            DEP                                                       28    100            (commercially                                             30    95.4           available    95                                           32    100            comparison)                                               37    100            Untreated    0                                            38    100            control                                                   39    99                                                                       40    96.4                                                                     ______________________________________                                    

EXAMPLE 16

By the methods of Examples 13 to 15, and as reported in Table 5 below, the compounds of this invention are shown to exhibit excellent activity against insects belonging to the Lepidoptera such as tobacco cutworm (Prodenia litura), rice stem borer (Chilo suppressalis), fall webworm (Hyphantria cunea) and the like, as compared with compounds of similar structure, identified by letters of the alphabet.

                                      Table 5                                      __________________________________________________________________________     Results of tests on harmful Lepidoptera insects                                __________________________________________________________________________                          Killing Ratio (%)                                                              Tobacco cutworm   Rice-stem                                                                            Fall webworm                                           (Prodenia litura) borer (Hyphantria cunea)                                     1000  300   100   250   1000  300   100                     Compounds          ppm   ppm   ppm   ppm   ppm   ppm   ppm                   __________________________________________________________________________      ##STR33##                                                                     30                   10    0     0     0     0     0                            ##STR34##                                                                     100                  100   100   100   100   100   100                          ##STR35##                                                                     0                    0     0     0     40    0     0                            ##STR36##                                                                     30                   5     0     0     0     0     0                            ##STR37##                                                                     100                  100   100   100   100   100   100                          ##STR38##                                                                     10                   0     0     0     50    0     0                            ##STR39##                                                                     0                    0     0     0     0     0     0                            ##STR40##                                                                     10                   0     0     0     20    0     0                            ##STR41##                                                                     100                  100   100   100   100   100   100                          ##STR42##                                                                     10                   0     0     0     0     0     0                            ##STR43##                                                                     40                   0     0     0     30    0     0                            ##STR44##                                                                     100                  100   100   100   100   100   90                           ##STR45##                                                                     50                   0     0     0     40    0     0                            ##STR46##                                                                     50                   0     0     0     40    0     0                            ##STR47##                                                                     100                  100   100   96.4  100   100   100                          ##STR48##                                                                     50                   0     0     0     50    0     0                            ##STR49##                                                                     30                   0     0     10    10    0     0                            ##STR50##                                                                     100                  100   100   100   100   80    60                           ##STR51##                                                                     10                   0     0     0     20    0     0                            ##STR52##                                                                     0                    0     0     0     0     0     0                            ##STR53##                                                                     0                    0     0     0     0     0     0                            ##STR54##                                                                     10                   0     0     0     0     0     0                            ##STR55##                                                                     100                  100   100   99    100   100   90                           ##STR56##                                                                     10                   0     0     0     10    0     0                            ##STR57##                                                                     20                   0     0     0     10    0     0                            ##STR58##                                                                     60                   20    0     12.3  30    0     0                            ##STR59##                                                                     100                  100   100   98.6  100   100   90                           ##STR60##                                                                     20                   0     0     0     0     0     0                            ##STR61##                                                                     20                   0     0     0     0     0     0                            ##STR62##                                                                     100                  100   100   100   100   90    40                          __________________________________________________________________________

EXAMPLE 17

Test against Green peach aphids (Myzus persicae) and Hop aphid (Phorodon humuli) (contact action)

Solvent: 3 parts by weight of aceotn

Emulsifier: 1 part by weight of alkyl aryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage plant infested with each aphids are sprayed with the preparation of the active compound until dripping wet. After 24 hours, the degree of destruction is determined as a percentage: 100% means that all the aphids are killed whereas 0% means that none are killed.

The results are shown in Table 6.

                                      Table 6                                      __________________________________________________________________________     Results of tests on Green peach aphid and Hop aphid                            __________________________________________________________________________                        Concen                                                                         tration                                                                              Green peach                                                              of a.i.                                                                              aphid   Hop aphid                                                        (%)   A   B   A   B                                         __________________________________________________________________________      ##STR63##                                                                     0.1 0.02 0.004 0.0008 0.00016                                                                     100% 100 100  90  5                                                                  -- 100 100  100  93                                                                100% 100 100  90  25                                                               -- 100% 100 100 100                           Compound No. 13 of the                                                                            0.000032                                                                             --   0  --   93                                       present invention                                                               ##STR64##                                                                     0.1 0.02 0.004 0.0008  0.00016                                                                    100% 100 100  80  30                                                                 -- 100% 100  75   50                                                               100% 100  80  50  25                                                               -- 100% 100 100  93                           Compound No. 26 of the                                                                            0.000032                                                                             --   5  --  70                                        present invention                                                               ##STR65##                                                                     0.1 0.02 0.004 0.0008 0.00016                                                                      85%  80  70  15  5                                                                  -- 100%  98  70  40                                                                 85%  70  40  25  10                                                               -- 100% 100  98  80                           Commercial control:                                                                               0.000032                                                                             --   10 --  30                                        lebaycid (D)                                                                   __________________________________________________________________________       *A: Resistance-acquired Green peach aphid and Hop aphid                       **B: Green peach aphid and Hop aphid without resistance                  

EXAMPLE 18

Carmine mite or two-spotted spider mite (Tetranychus telarius test)

Testing method:

A haricot bean having two developing leaves planted in a 6 cm diameter pot was infected with 50-100 imagines and nymphs of carmine mite. Two days after the infection, 40 ml of the preparation of the active compound diluted to the prescribed concentration prepared in the same manner as in Example 13 were sprayed on to the pot. The pot was kept in a greenhouse for 10 days, and the control effect was evaluated. The evaluation is expressed by an index of the following scale:

Control Effect Index

3: No living imago or nymph

2: Less than 5% of living imagines and nymphs based on the untreated control

1: 6-50% of living imagines and nymphs based on the untreated control

0: more than 51% of living imagines and nymphs based on the untreated control

The results are shown in Table 7.

                  Table 7                                                          ______________________________________                                         Test results against Tetranychus telarius larvae                               ______________________________________                                                      Control Effect                                                    Compound     Active Ingredient Concentration                                   No.          1000 ppm   300 ppm   100 ppm                                      ______________________________________                                         13           3          3         3                                            16           3          3         2                                            17           3          3         2                                            20           3          3         3                                            21           3          3         3                                            23           3          3         2                                            24           3          3         2                                            44           3          3         2                                            49           3          3         3                                            CPCBS*                                                                         (comparison) 3          2         0                                            CMP**                                                                          (comparison) 3          1         0                                            Untreated Control                                                                           0          0         0                                            ______________________________________                                           *CPCBS (Wettable Powder): p-chlorophenyl-p'chlorobenzenesulfonate 36%:        bis(4-chlorophenoxy)metan 14%                                                  **CMP: O,O-diethyl-S-(2,5-dichlorophenylmercaptomethyl) dithiophosphate  

EXAMPLE 19

House fly (Musca domestica) test

Testing method:

1 ml of an emulsion of the active compound diluted to the prescribed concentration prepared in the same manner as in Example 13 was applied on to a filter paper placed in a Petri dish of 9 cm diameter. 10 mature female adult house flies were then placed in the dish and the dish was kept in a constant temperature chamber at 28° C. After 24 hours, the number of dead insects was counted and the killing ratio was calculated.

The results are shown in Table 8.

                  Table 8                                                          ______________________________________                                         Test results against Musca domestica adults                                    ______________________________________                                                    Killing Ratio (%)                                                              Active Ingredient Concentration                                     Compound     1000       100       10                                           No.          ppm        ppm       ppm                                          ______________________________________                                         13           100        100       80                                           14           100        100       --                                           15           100        100       --                                           16           100        100       --                                           18           100        100       --                                           19           100        100       --                                           20           100        100       --                                           21           100        100       --                                           40           100        100       --                                           41           100        100       --                                           49           100        100       70                                           50           100        100       80                                           62           100        100       --                                           DEP (comparison)                                                                            100        100       --                                           Untreated Control                                                                            0          0         0                                           ______________________________________                                    

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention. 

What is claimed is:
 1. A method of combatting insects, acarids, or nematodes which comprises applying to the insects, acarids or nematodes or to an insect, acarid or nematode habitat an insecticidally, acaricidally or nematocidally effective amount of a phosphoric acid ester of the formula ##STR66## wherein at least one X is nitro, cyano, lower alkylmercapto, lower alkylsulfinyl, lower alkoxycarbonyl, or lower alkylcarbonyl, and the others if present may also be halogen or lower alkyl, and m is 1, 2 or
 3. 2. The method according to claim 1, wherein such compound is O-ethyl-O-(4-methylmercaptophenyl)-S-n-propyl phosphorothiolate of the formula ##STR67##
 3. The method according to claim 1, wherein such compound is O-ethyl-O-(4-nitrophenyl)-S-n-propyl phosphorothiolate of the formula ##STR68##
 4. The method according to claim 1, wherein such compound is O-ethyl-O-(4-cyanophenyl)-S-n-propyl phosphorothiolate of the formula ##STR69##
 5. The method according to claim 1, wherein such compound is O-ethyl-O-(3-methyl-4-methylmercaptophenyl)-S-n-propyl phosphorothiolate of the formula ##STR70##
 6. The method according to claim 1, wherein such compound is O-ethyl-O-(3-methyl-4-nitrophenyl)-S-n-propyl phosphorothiolate of the formula ##STR71##
 7. The method according to claim 1, wherein such compound is O-ethyl-O-(2-methyl-4-methylmercaptophenyl)-S-n-propyl phosphorothiolate of the formula ##STR72##
 8. The method according to claim 1, wherein such compound is O-ethyl-O-(3,5-dimethyl-4-methylmercaptophenyl)-S-n-propyl phosphorothiolate of the formula ##STR73##
 9. An insecticidal, acaricidal or nematocidal composition containing as active ingredient an insecticidally, acaricidally or nematocidally effective amount of a phosphoric acid ester of the formula ##STR74## wherein at least one X is nitro, cyano, lower alkylmercapto, lower alkylsulfinyl, lower alkoxycarbonyl, or lower alkylcarbonyl, and the others if present may also be halogen or lower alkyl, and m is 1, 2 or 3,in admixture with a pesticide diluent.
 10. A composition according to claim 9 in which said compound is:O-ethyl-O-(4-methylmercaptophenyl)-S-n-propyl phosphorothiolate, O-ethyl-O-(4-nitrophenyl)-S-n-propyl phosphorothiolate, O-ethyl-O-(4-cyanophenyl)-S-n-propyl phosphorothiolate, O-ethyl-O-(3-methyl-4-methylmercaptophenyl)-S-n-propyl phosphorothiolate, O-ethyl-O-(3-methyl-4-nitrophenyl)-S-n-propyl phosphorothiolate, O-ethyl-O-(2-methyl-4-methylmercaptophenyl)-S-n-propyl phosphorothiolate, O-ethyl-O-(3,5-dimethyl-4-methylmercaptophenyl)-S-n-propyl phosphorothiolate. 